EP0081790A1 - p-Phenylene diamines, their preparation and use - Google Patents

Abstract

p-Phenylenediamines of the general formula <IMAGE> in which R<1> represents a radical -(CHR<2>-CHR<2>-O)n-H or <IMAGE> where R<2> and R<5> represent hydrogen or alkyl groups having 1-4 carbon atoms, R<3> and R<4> represent alkyl groups having 1-4 carbon atoms and n represents integers from 1-4, and in which X represents a fluorine atom or, if R<1> represents an aminoalkyl group, a hydrogen atom are novel developer substances for oxidative hair dyes. They are prepared by reacting 1,2-difluoro-4-nitrobenzene with a polyglycolamine or by reacting p-fluoronitrobenzene with N<1>,N<1>-dialkyl-1,2-propanediamine, followed by catalytic hydrogenation of the resulting p-nitrophenylamines. Oxidative hair dyes with the novel developer substances and the customary coupling substances are distinguished by intensive, natural shades with good fastness properties and good dermatological acceptability.

Description

The invention relates to new p-phenylenediamines and hair colorants which contain them as a developer component.

The so-called oxidation colors, which result from the oxidative coupling of a developer component with a coupler component, play a preferred role for dyeing hair because of their intense colors and very good fastness properties. Nitrogen bases, such as p-phenylenediamine derivatives, diaminopyridines, 4-amino-pyrazolone derivatives and heterocyclic hydrazones, are usually used as developer substances. As so-called coupler components, m-phenylene diamine derivatives, phenols, naphthols, resorcinol derivatives and pyrazolones are mentioned.

• Sie müssen bei der oxidativen Kupplung mit den jeweiligen Entwickler- bzw. Kupplerkomponenten die gewünschten Farbnuancen in ausreichender Intensität ausbilden. Sie müssen ferner ein ausreichendes bis sehr gutes Aufziehvermögen auf menschlichem Haar besitzen und sie sollen darüber hinaus in toxikologischer und dermatologischer Hinsicht unbedenklich sein.

Good oxidation hair dye components primarily have to meet the following requirements:

• You have to develop the desired color shades with sufficient intensity in the oxidative coupling with the respective developer or coupler components. They must also have sufficient to very good absorbency on human hair and they should also be safe from a toxicological and dermatological point of view.

The compound class of substituted or unsubstituted p-phenylenediamines, which is usually used as developer substance, has the disadvantage that it causes sensitization in a number of people and, as a result, severe allergies. The developer substances proposed in recent times for avoiding these dermatological disadvantages cannot always be completely satisfactory in their application properties.

When searching for usable oxidation hair dyes, the task was therefore to find suitable components which optimally meet the aforementioned requirements.

1 in der R für einen Polyalkoholrest der Formel ⁅CHR² - CHR²-O⁆_n H oder eine Aminoalkylgruppe der Formel -CHR^3-

steht, wobei R² und R⁵ ein Wasserstoffatom oder eine Alkylgruppe mit 1 - 4 Kohlenstoffatomen, R³ und R⁴, eine Alkylgruppe und 1 - 4 Kohlenstoffatomen und n eine ganze Zahl von 1 - 4 bedeutet, und in der X für ein Fluoratom oder wenn R für eine Aminoalkylgruppe steht für ein Wasserstoffatom steht, sowie ein Verfahren zu deren Herstellung. Ein weiterer Gegenstand der Erfindung sind Haarfärbemittel, welche eine p-Phenylendiamin-Verbindung der Formel (I) als Entwicklerkomponente neben den in Oxidationshaarfarben üblichen Kupplerkomponenten und Träger- und Hilfsstoffen enthalten. Anstelle der p-Phenylendiaminderivate der Formel I können in den Haarfarben auch deren anorganische oder organische Salze eingesetzt werden.New p-phenylenediamine derivatives have now been found which, as developer substances with the coupling components customary in oxidation hair colors, meet the requirements to a particularly high degree. The invention relates to p-phenylenediamines of the formula I.

1 in the R for a polyalcohol radical of the formula ⁅CHR ² - CHR ² -O⁆ _n H or an aminoalkyl group of the formula -CHR ^3-

stands, wherein R ² and R ^{5 is} a hydrogen atom or an alkyl group with 1-4 carbon atoms, R ³ and R ⁴ , an alkyl group and 1-4 carbon atoms and n represents an integer of 1-4, and in which X represents a fluorine atom or when R represents an aminoalkyl group represents a hydrogen atom stands, as well as a process for their preparation. The invention further relates to hair colorants which contain a p-phenylenediamine compound of the formula (I) as developer component in addition to the coupler components and carriers and auxiliaries customary in oxidation hair colors. Instead of the p-phenylenediamine derivatives of the formula I, their inorganic or organic salts can also be used in the hair colors.

The derivatives of the formulas II and III are particularly preferred as developer components.

When used as developer components, the compounds according to the invention, with the coupler substances generally used for oxidation hair coloring, provide the most varied, very intense color shades and thus represent a significant enrichment of the oxidative hair coloring possibilities. In addition, the hydroxyalkylated alkylamino-p-phenylenediamines are distinguished by very good fastness properties of the dyeings achieved with it, through good solubility in water, good storage stability and toxicological and dermatological harmlessness.

The hydroxyalkylated alkylamino-p-phenylenediamines to be used according to the invention as developer components can either as such or in the form of their salts with inorganic or organic acids, such as, for. B. as chlorides, sulfates, phosphates, acetates, propionates, lactates, citrates.

To prepare the 2-fluoro-N-polyether alcohol-p-phenylenediamines according to the invention, 1,2-difluoro-4-nitrobenzene is mixed with di- or polyglycolamide in the first stage and reacted at an elevated temperature, preferably 1 _{00-14 0} ° C. and then poured onto ice water. The oil which separates out is preferably extracted with ether, and the extractant is removed distilled and the N- (2-fluoro-4-aminophenyl) -di or polyglycolamine obtained in a second stage in the presence of a hydrogenation catalyst, preferably Raney nickel, hydrogenated.

To prepare N- (p-aminophenyl) -N'-dialkyl-1,2-di-aminoalkane, in a first step N ¹ , N ^1- dialkyl-1,2-dialkanediamine in dimethylformamide with potassium carbonate at elevated temperature with preferably implemented equimolar amount of p-fluoronitrobenzene. After several hours of reaction time at 12o-18o, preferably 15 ₀ - 16 ₀ ° C, the mixture is poured onto ice water, the separated oil is extracted and the extractant is distilled off. The N- (p-nitrophenyl) -N'-dialkyl-1,2-diaminoalkane obtained is hydrogenated in a second stage in the presence of a hydrogenation catalyst.

The developer components according to the invention can be used with a wide variety of substances known as coupler components, such as α-naphthol, o-cresol, m-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, pyrocatechol, pyrogallol, 1,5- or 1,7-dihydroxynaphthalene , 5-amino-2-methylphenol, m-aminophenol, 2,4-diaminoanisole, m-toluenediamine, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 1-amino-3-acetyl - acetamino-4-nitrobenzene, 1-amino-3-cyanoacetylamino-3-nitrobenzene, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 2 -Chlor-6-methyl-3-aminophenol, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 2,4-diaminophenol and 2,4-dichloro-3-isopropylidene aminophenol, to be converted into hair dyes.

In the hair colorants according to the invention, the developer components are generally approximately molar Amounts based on the coupler substances used. Even if the molar use proves to be expedient, it is not disadvantageous if the developer component is used in a certain excess or deficit.

Furthermore, it is not necessary for the developer component and the coupler substance to be uniform products; rather, both the developer component can be a mixture of the hydroxyalkylated alkylamino-p-phenylenediamines to be used according to the invention and the coupler substance can be mixtures of the abovementioned coupler components.

In addition, the hair colorants according to the invention can contain other known and customary developer components, and also, if appropriate, customary direct dyes in the mixture, if this is necessary to achieve certain color nuances.

The oxidative coupling, i. H. the development of the coloring, in principle, as with other oxidation hair dyes, can take place through atmospheric oxygen. However, chemical oxidizing agents are expediently used. In particular, hydrogen peroxide or its adducts with urea, melamine and sodium borate, as well as mixtures of such hydrogen peroxide additive compounds with potassium peroxide disulfate come into consideration as such.

The hair colorants according to the invention are incorporated for use in appropriate cosmetic preparations such as creams, emulsions, gels or simple solutions and immediately before use on the Hair with one of the oxidizing agents mentioned. The concentration of such dye preparations on coupler-developer combination is 0.2 to 5 percent by weight, preferably 1-3 percent by weight. To prepare creams, emulsions or gels, the dye components are mixed with the other constituents customary for such preparations. As such additional components are such. B. wetting or emulsifying agents of the anionic or non-ionic type, such as alkylbenzenesulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid alkanolamides, adducts of ethylene oxide with fatty alcohols, thickeners such as methyl cellulose, starch, higher fatty alcohols, paraffin oil, fatty acids, furthermore perfume oils and hair care agents, such as pantothelic agents, such as pantothelic agents such as call. The additives mentioned are used in the usual amounts for these purposes, such as. B. wetting and emulsifying agents in concentrations of o, 5-30 percent by weight and thickeners in concentrations of o, 1-25 percent by weight, each based on the entire preparation.

Regardless of whether it is a solution, an emulsion, a cream or a gel, the hair colorants according to the invention can be used in a weakly acidic, neutral or, in particular, alkaline medium at a pH of 8-1o. The application temperatures range from 15 to 4o C. After an exposure time of approx. 3o minutes, the hair dye is removed from the hair to be colored by rinsing. The hair is then washed with a mild shampoo and dried.

It can be achieved very intense and natural colors, preferably brown to _D unkel blue tones. The dyes have good light, wash and rub fastness properties and can be easily removed with reducing agents.

The following examples are intended to explain the subject matter of the invention in more detail, without restricting it thereto.

example 1 Production of N- (2-fluoro-aminophenyl) diglycolamine dihydrochloride step 1 N- (2-fluoro-4-nitrophenyl) diglycolamine

• Ausbeute: 16,7 g gelbes öl
• IR-Spektrum (cm^-1): 1615, 1545, 15oo, 137₀, 1330, 1300, 1195, 115o, 1125, 1₀7₀, 945, 880, 8o5

0.06 mol (10 g) of 1,2-difluoro-4-nitrobenzene are mixed with 0.13 mol (13.7 g) of diglycolamine. The mixture is heated to 11 ₀ ° C and poured onto about 1oo ml ice-water after 1.5 hours. The separated oil is extracted with ether. After drying over sodium sulfate, the ether is distilled off.

• Yield: 16.7 g of yellow oil
• IR spectrum (cm ^-1 ): 1615, 1545, 15oo, 137 ₀ , 1330, 1300, 1195, 115o, 1125, 1 ₀ 7 ₀ , 945, 880, 8o5

Level 2 N- (2-fluoro-4-aminophenyl) diglycolamine dihydrochloride

• Ausbeute: 14,3 g farblose Kristalle; Fp. 146° C.

10 g (0.065 moles) of N- (2-fluoro-4-nitrophenyl) diglycolamine are hydrogenated in 100 ml of ethanol in the presence of Raney nickel (approx. 1 g) at room temperature and 1 atm. When the H ₂ uptake has ended, the catalyst is filtered off. The solution is acidified with hydrochloric acid and evaporated to dryness.

• Yield: 14.3 g of colorless crystals; Mp 146 ° C.

Example 2 Preparation of N- (p-aminophenyl) -N'-dimethyl-1,2-diaminopropane trihydrochloride step 1 N- (p-nitrophenyl) -N'-dimethyl-1,2-diaminopropane

• Ausbeute: 16 g gelbes Öl.

To a suspension of 9.5 g (o, o9 mol) of N ¹ , N ^1- dimethyl-1,2-propanediamine in 20 ml of dimethylformamide and 8.3 g ( ₀ , ₀ 6 mol) of potassium carbonate at 90 ° C 13 , 1 g (o, o9 mol) of p-fluoronitrobenzene was added dropwise. After 4 hours at 160 ° C., the mixture is cooled and poured onto 250 ml of ice water. The separated oil is extracted with ethyl acetate. After drying over sodium sulfate, the mixture is evaporated to dryness.

• Yield: 16 g of yellow oil.

Level 2 N- (p-aminophenyl) -N'-dimethyl-1,2-propanediamine trihydrochloride

• Ausbeute: 16 g weiße Kristalle
• IR-Spektrum (cm 1): 1630, 1610, 1570, 151o, 1480, 1465, 132₀, 1260, 1190, 1130, 1065, 1₀18, 1000, 980, 920, 820.

16.2 g of N- (p-nitrophenyl) -N'-dimethyl-1,2-propanediamine are hydrogenated in 200 ml of ethanol in the presence of 5% palladium on carbon at 25 ° C. and 1 atm. When the H ₂ uptake has ended, the catalyst is filtered off, acidified with dilute hydrochloric acid and evaporated to dryness.

• Yield: 16 g of white crystals
• IR spectrum (cm 1): 1630, 1610, 1570, 151o, 1480, 1465, 132 ₀ , 1260, 1190, 1130, 1065, 1 ₀ 18, 1000, 980, 920, 820.

Example 3

• 1o Gewichtsteilen Fettalkoholen der Kettenlänge C₁₂-C₁₈
• 1o Gewichtsteilen Fettalkoholsulfat (Natriumsalz) Kettenlänge ^C ₁₂ ^-C ₁₈
• 75 Gewichtsteilen Wasser

The p-phenylenediamines prepared according to Examples 1 and 2 were used in hair dye in the form of a cream emulsion for dyeing tests. They were made into an emulsion

• 1o parts by weight of fatty alcohols with chain length C ₁₂ -C ₁₈
• 10 parts by weight of fatty alcohol sulfate (sodium salt) chain length ^C ₁₂ ^-C ₁₈
• 75 parts by weight of water

in each case o, o1 mol of the p-phenylenediamine derivatives according to the invention and the coupler substances listed below are incorporated. The pH of the emulsion was then adjusted to 9.5 using ammonia and the emulsion was made up to 100 parts by weight with water. The oxidative coupling was carried out with 9% hydrogen peroxide solution as the oxidizing agent, 10 parts by weight of the hydrogen peroxide solution being added to 100 parts by weight of the emulsion. The respective coloring cream with additional oxidizing agent was applied to 90% gray, not particularly pretreated human hair and left there for 30 minutes. After the dyeing process had ended, the hair was washed out with a customary shampoo and then dried. The dyeings obtained are shown in Table I below.

• 1. Resorcin
• 2. 4-Chlorresorcin
• 3. 1-Naphthol
• 4. 5-Amino-2-methylphenol
• 5. 1,3-Bis-(2,4-diaminophenoxy)-propan
• 6. 1-Phenyl-3-acetamido-pyrazolon-5
  

The following compounds served as coupler substances:

• 1. Resorcinol
• 2. 4-chlororesorcinol
• 3. 1-naphthol
• 4. 5-amino-2-methylphenol
• 5. 1,3-bis (2,4-diaminophenoxy) propane
• 6. 1-phenyl-3-acetamido-pyrazolon-5
  

Claims (9)

1. p-phenylenediamines of the general formula T.

in which R ^{1 is} a polyalcohol radical of the formula ⁅CHR ² -CHR ² -O⁆ _n H or an aminoalkyl group of the formula -CHR ³ -CHR ²

is where R ² and R ^{5 is} a hydrogen atom or an alkyl group having 1-4 carbon atoms, R ³ and R ⁴ , an alkyl group and 1-4 carbon atoms and n is an integer from 1-4, and in which X is a fluorine atom or when R ^{1 represents} an aminoalkyl group represents a hydrogen atom. 2. N- (2-fluoro-4-aminophenyl) diglycolamine. 3. N- (p-aminophenyl) -N'-dimethyl-1,2-diaminopropane. 4. Process for the preparation of p-phenylenediamine compounds of the general formula IV

in the round n have the meaning given above, characterized in that 1,2-difluoro-4-nitrobenzene is reacted with a polyglycolamine at elevated temperature and the reaction product is separated off by extraction and hydrogenated in the presence of a hydrogenation catalyst. 5. Process for the preparation of a p-phenylenediamine compound of formula V

where R ² , R ³ , R ⁴ and R ^{5 have} the abovementioned meaning, characterized in that N ¹ , N ^1- dimethyl-1,2-propanediamine is reacted in dimethylformamide, potassium carbonate and p-fluoronitrobenzene at elevated temperature, the reaction product is separated off by extraction and hydrogenated in the presence of a hydrogenation catalyst. 6. Hair colorants based on oxidation dyes, characterized by a content of a p-phenylenediamine compound of the formula (I), and also their inorganic or organic salts as developer components and the coupler substances, carriers and auxiliaries customary in oxidation hair colors. 7. Hair dye according to claim 6, characterized by a content of N- (2-fluoro-4-aminophenyl) diglycolamine or its inorganic or organic salts as developer component. 8. Hair dye according to claim 6, characterized by a content of N- (p-aminophenyl) -N'-dimethyl-1,2-diaminopropane or its inorganic or organic salts as developer component. 9. Hair dye according to claim 6 to 8, characterized by a content of developer-coupler combination of o, 2 to 5 weight percent, preferably 1 to 3 weight percent, based on the total agent.